Denatured alcohol and ester



Patented Feb. 27, 1934 UNITED STTES ATENT OFFICE.

DENATURED ALCOHOL AND ESTER William N. Davis and John T.

Rutherford,

No Drawing. Application August 8, 1932 Serial No. 628,003

9 Claims.

This invention relates to the production of denatured organic liquids,such as alcohols and esters.

In the co-pending application of John T.

Rutherford, Serial No. 628,004, filed August 8,

1932, covering Sulphur dioxide extracts of petroleum and processes ofsecuring the same, there is described the production of certain newproducts from petroleum secured by subjecting petroleum oil to a doubleextraction process with sulphur dioxide. We have discovered that thesulphur dioxide extracts of petroleum, both those described in saidco-pending application and others resulting from a single extraction,may be used with advantage in the denaturing of organic liquids, such asalcohols and esters.

The extracts of petroleum derived by treating petroleum with sulphurdioxide contain unsaturated, aromatic, and sulphur containing bodies ingreater amounts than are normally present in petroleum oil. It has beendiscovered that these aromatic, unsaturated and sulphur bearing oils areof value in denaturing organic liquids, such as alcohols. The extractsof petroleum obtained by treating petroleum with sulphur dioxide containa wide range of boiling points and, therefore, can not be removed fromorganic liquids, such as ordinary alcohol, by normal processes 'ofdistillation and rectification. Petroleum oil generally is notsufficiently miscible with alcohol, especially in dilute form, to befully satisfactory as a denaturant. It has been found, however, thatthese sulphur dioxide extracts of petroleum are much more miscible withalcohol both in concentrated and relatively dilute form. The sulphurdioxide extracts have also a distinctive odor and a disagreeable tastein excess of that of petroleum oils generally, but preserveapproximately the same non-toxic properties. These points render sulphurdioxide extracts more suitable than regular petroleum oils for use asalcohol denaturants or as denaturants of other organic liquids.

It is a general object of the present invention, therefore, to providean organic liquid denatured through the use of a sulphur dioxide extractof petroleum.

It is further found that sulphur dioxide extracts of petroleum areuseful in denaturing alcohols as solvents or diluents for otherdenaturants. Thus, in denaturing alcohols with the acid oils derivedfrom the sulphuric acid sludges of petroleum, as described in theco-pending application of William H. Hampton, Serial No. 508,369, filedJanuary 12, 1931, it is frequently desired to add a diluent. We havediscovered that sulphur dioxide extracts of petroleum may be used asadiluent and solvent for these acid oils in connection with their use asorganic liquid denaturants.

The present invention, together with various objects and advantagesthereof will best be understood from a description of a preferred formor forms of products embodying the invention. For this purpose, there ishereafter described a preferred form of denatured alcohol and process ofproducing the same.

In one example of the invention, a crude pressure naphtha obtained fromthe pyrogenetic cracking of California fuel oil was first topped orreduced to a 200 F. initial boiling point. This topped pressure naphthawas treated with twice its volume of liquid sulphur dioxide, accordingto the ordinary Edeleanu method. The topped naphtha before treatment hadthe following characteristics:

Gravity A. P. I 47.3 Initial boiling point 208 F. 20% 250 F. 50% 280 F.30 90% 386 F. Final boiling point 506 F. Per cent sulphur .73 C/H ratio85.l0/l3.27 Miscibility with an equal volume of 95% ethyl alcoholComplete above 87 F.

After contact of such topped crude pressure naphtha with'sulphurdioxide, the hydrocarbon and liquid sulphur dioxide layers areseparated. The liquid sulphur dioxide layer was then heated 90 forevaporation of its sulphur dioxide content, and there was secured as anextracted product an oil equal to 68.5% of the original naphtha treated.

This extract had the following properties:

' It will be seen that the extracted product be-' cause of its greateralcohol solubility and the concentration of aromatic, unsaturated andsulphur compounds is an excellent material for use in denaturingalcohols and may be added for that 110 purpose to alcohol in amounts upto 5%. It is difficult or impossible to separate by distillation, andwhen added to 95% alcohol in 1 ,5 percentage,

a denaturant for alcohol may also be used for denaturing other organicliquids, such; for example, as ethyl esters, in which case it may beused in .amounts as low as one-eighth of 1%, by volume.

It also may be used in combination with other denaturing materials fororganic liquids. For example, the acid oils derived by hydrolysis ofacid sludge resulting-from the sulphuric acid treatment of petroleumwhich are in themselves excellent denaturing materials.

For example, by treating gasoline or kerosene distillates withconcentrated sulphuric acids a sulphuric acid sludge is formed, whichwhen hydrolyzed in a retort under temperature and pressure, for example290 F. and 20 lbs. pressure, will yield an acid in one layer and an acidoil or tail as an upper layer. This acid oil or tail, preferablyre-distilled to give av fraction of desired range of boiling points,preferably boiling between say 100 F. and 450 F., although in certaincases higher and lower boiling points may be ineluded, has been found tobe a most effective denaturant due principally to the relatively highcontent of sulphur bodies which are in the neighborhood of 5 to 10%. Itis frequently desirable with these denaturants derived from acid sludgeto use a diluent. When ordinary petroleum oil is employed as a diluent,turbidity appears upon addition of water when the strength of thealcohol is reduced to 15%.

By employing the sulphur dioxide extracts of petroleum, it is found thatno turbidity appears in the denatured alcohol until the strength of thealcohol is reduced to about While the aforementioned product derived.

from extracting a light petroleum oil once with sulphur dioxide is anexcellent denaturant, either alone or in combination with otherdenaturants, it has been discovered that a denaturant of still superiorproperties may be derived by first subjecting the extract to furthertreatment before it is used as a denaturant.

For this purpose, the extract thus obtained may be blended with an equalproportion of a refined oil. The refined oil is of a different range ofboiling points than the extract. The mixed refined oil and sulphurdioxide extract is then treated with twice its volume of liquid sulphurdioxide. Upon settling, there is secured a separation of hydrocarbon andliquid sulphur dioxide layers. The liquid sulphur dioxidelayer isseparated from the hydrocarbon and treated for the removal of thesulphur dioxide, thereby producing an extracted product of petroleum.When this extracted product is re-distilled to secure substantially thesame boiling point range as the original pressure naphtha, ,a yield of37.6%of extracted and re-distilled product is obtained, which'uponneutralizing possess the following properties:

Gravity A. P. I 36. 3

Initial boiling point 257 F.

20% 299 F. 50% 366 F. 90% 403 F.

Final boiling point 447 F. Per cent sulphur 1. 93 C/H ratio 87. 1/11. 9Miscibility with an equal portion of 95% ethyl alcohol Complete above 58F. A product obtained by this double extraction contains a furtherdegree of concentration of unsaturates and aromatics. It has greateralcohol solubility, and when used as a denaturant of alcohols thealcohol will stand a greater water dilution before turbidity appears.

In addition to the use of the extracts obtained by these doubleextraction processes described, the extract maybe subject to one or moreadditional extractions with sulphur dioxide-in a likemanner to thatdescribed in connection with the second extraction. The alcoholsolubility of the prodnot and the concentration of aromatic, unsaturatedand sulphur compounds will correspondingly increase andthe value of theproduct as a denaturant for alcohols or other organic liquids will alsoincrease.

It is not necessary in producing the sulphur di oxide extract to be usedin the denatured alcohol that one start with a naphtha or gasoline cutof petroleum, as certain kerosene distillates may also be employed andyield extracted oils of value as a denaturant.

While the particular denatured organic liquids herein described and theprocess of producing the same are well adapted to carry out the objectsof the present invention, it is to be understood that variousmodifications and changes may be made without departing from theprinciple of the invention, as set forth in the appended claims.

1. A denatured alcohol or ester containing the extracted oils derived bythe sulphur dioxide extraction treatment of petroleum oils, said oilscontaining organic sulphur bodies and a relatively large amount ofunsaturated and aromatic constituents.

2. A denatured alcohol containing hydrocarbon oil as a denaturantcontaining a high carbon to hydrogen ratio and consisting largely ofunsaturated and aromatic constituents, said denaturant being theextracted oil derived from the extraction of petroleum oil with sulphurdioxide.

3. A denatured alcohol or ester containing as a denaturant an extractofpetroleum oil containing a high carbon to hydrogen ratio andconsisting largely of unsaturated and aromatic constituents, saidextract being derived from ex- 1 stituents, said extract being derivedfrom extracting petroleum oil with sulphur dioxide, the petroleum oilextracted havinga low range of boiling points.

5. A denatured alcohol comprising as a denaturant the extractedunsaturated and aromatic oils derived from a sulphur dioxide treatmentof kerosene or gasoline fractions of petroleum, said denaturantv oilscontaining organic sulphur bodies and having a boiling point range suchthat they cannot be removed from alcohol by ordinary distillation.

6. A denatured alcohol containing as a denaturant the extracted oilsderived from the sulphur dioxide treatment of kerosene or gasolinefractions of petroleum, said denaturant oils containing largepercentages of unsaturated and aromatic bodies and sulphur bodies, saiddenaturant oils having a. boiling point range such that they can not beremoved from alcohol by distillation,

said denaturant oils also being inseparable from alcohol byrefrigeration and filtering agents. h 7. A denatured alcohol includingas a denaturant the extracted oils derived from the extraction withsulphur dioxide of the extracted petroleum oils which are derivedfromextraction of petroleum with sulphur dioxide.-

8. A denatured organic liquid containing as a denaturant the extractedoils derived from a process of extracting petroleum oil with sulphurdioxide, the petroleum oil being the extracted oil resulting from aprevious process of extracting a petroleum oil with sulphur dioxide.

CERTIFICATE Patent No. l, 649, 244.

WILLIAM N.

9. A denatured alcohol or ester including as a denaturant the extractedoils derived from a process in which petroleum oil is first extractedwith sulphur dioxide, and the extracted fraction is thereafter againextracted from sulphur dioxide, the denaturant oils being the extractedprodnot of the second extraction.

WILLIAM N. DAVIS. JOHN T. RUTHERFORD.

or coRinzc'tioN.

February 27, 1934.

DAVIS, ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows:

Page 2, line 33, for

"15%" read and that the said Letters Patent should be read with thiscorrection therein that the same may conform to the record of the casein the Patent Office.

Signed and seaied this 15th day of May, A. D. 1934.

(Seal) Bryan M. Battey Acting Commissioner of Patents.

